CN114729245A - Adhesive composition for tire cord, tire cord and tire - Google Patents

Adhesive composition for tire cord, tire cord and tire Download PDF

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Publication number
CN114729245A
CN114729245A CN202180006471.1A CN202180006471A CN114729245A CN 114729245 A CN114729245 A CN 114729245A CN 202180006471 A CN202180006471 A CN 202180006471A CN 114729245 A CN114729245 A CN 114729245A
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CN
China
Prior art keywords
adhesive composition
tire
tire cord
polyurethane resin
cord
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202180006471.1A
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Chinese (zh)
Inventor
李成揆
全玉花
李闵镐
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kolon Industries Inc
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Kolon Industries Inc
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Publication date
Application filed by Kolon Industries Inc filed Critical Kolon Industries Inc
Publication of CN114729245A publication Critical patent/CN114729245A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
    • B60C9/0042—Reinforcements made of synthetic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0041—Compositions of the carcass layers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0847—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers
    • C08G18/0852—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers the solvents being organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
    • C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3228—Polyamines acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J119/00—Adhesives based on rubbers, not provided for in groups C09J107/00 - C09J117/00
    • C09J119/02—Latex
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/44—Yarns or threads characterised by the purpose for which they are designed
    • D02G3/48—Tyre cords
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
    • B60C9/02—Carcasses
    • B60C9/04—Carcasses the reinforcing cords of each carcass ply arranged in a substantially parallel relationship
    • B60C2009/0416—Physical properties or dimensions of the carcass cords
    • B60C2009/0425—Diameters of the cords; Linear density thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
    • B60C9/02—Carcasses
    • B60C9/04—Carcasses the reinforcing cords of each carcass ply arranged in a substantially parallel relationship
    • B60C2009/0416—Physical properties or dimensions of the carcass cords
    • B60C2009/0466—Twist structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
    • B60C9/02—Carcasses
    • B60C9/04—Carcasses the reinforcing cords of each carcass ply arranged in a substantially parallel relationship
    • B60C2009/0475—Particular materials of the carcass cords
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C08G2170/80—Compositions for aqueous adhesives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/354—Applications of adhesives in processes or use of adhesives in the form of films or foils for automotive applications
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2421/00—Presence of unspecified rubber
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2463/00—Presence of epoxy resin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2475/00—Presence of polyurethane
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2505/00—Industrial
    • D10B2505/02—Reinforcing materials; Prepregs
    • D10B2505/022—Reinforcing materials; Prepregs for tyres

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Textile Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Tires In General (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The present invention relates to an adhesive composition for a tire cord comprising an adhesive layer formed of the above adhesive composition, a latex, an alicyclic polyurethane resin having a weight average molecular weight (Mw) of 250,000 to 350,000, an amine compound, and water, a tire comprising the above tire cord, and a tire.

Description

Adhesive composition for tire cord, tire cord and tire
Technical Field
The present invention relates to an adhesive composition for a tire cord, a tire cord and a tire.
Background
In order to reinforce the strength of the rubber structure, a fiber reinforcement is used. For example, in a rubber tire, polyester fibers, polyamide fibers, aramid fibers, polyvinyl alcohol fibers, or the like may be used as the reinforcing material. Also, in some cases, the adhesion between the fiber and the rubber is not good according to the fiber, and therefore, an adhesive is coated on the surface of the fiber to supplement the adhesion between the fiber and the rubber. For example, in order to improve the adhesive strength between polyester fibers (raw cords) for tire cords and tire rubbers, an adhesive is coated on the polyester fibers.
Generally, among the adhesives used for the above purpose, rubbers (or latexes) containing resorcinol-formaldehyde or components derived therefrom are included. However, RF, which contains resorcinol (a phenol) and formaldehyde, known as carcinogens, is known to be harmful to humans. Moreover, for RF-containing adhesive waste liquids, specific post-management and post-treatment costs are generally required.
Meanwhile, as a method of coating the above adhesive composition on the fiber-reinforced material, dipping or spraying may be considered. In this preparation process, the respective components constituting the adhesive composition should be uniformly mixed and dispersed in the solvent contained in the composition. Also, even after impregnating or spraying a composition in which the respective components are uniformly mixed and dispersed, the composition should be uniformly coated on the surface of the fiber reinforced material in an appropriate amount. If the components of the composition are not sufficiently mixed or the fluidity of the composition is excessively increased due to the excessive use of the solvent, the adhesive strength cannot be secured.
Disclosure of Invention
Technical problem
An object of the present invention is to provide an environmentally friendly adhesive composition for a tire-cord, which can significantly improve the adhesive strength and heat-resistant adhesive strength between a tire rubber and a tire-cord.
It is another object of the present invention to provide a tire-cord having high adhesive strength and heat-resistant adhesion to a tire rubber, and therefore, capable of improving the durability of a tire.
It is still another object of the present invention to provide a tire comprising the above tire cord.
Technical scheme
The invention herein provides an adhesive composition for tire cords comprising: an epoxy compound; a latex; an alicyclic polyurethane resin having a weight average molecular weight (Mw) of 250,000 to 350,000; an amine compound; and water.
The present invention also provides a tire cord comprising: a fibrous substrate; and an adhesive layer formed on the fiber substrate, and the adhesive layer is formed of the above adhesive composition for a tire cord.
The present invention also provides a tire cord comprising: a fibrous substrate; and an adhesive layer formed on the fiber substrate, and including an epoxy compound, a latex, an alicyclic polyurethane resin having a weight average molecular weight (Mw) of 250,000 to 350,000, and an amine compound.
The invention also provides a tire comprising the tire cord.
Hereinafter, the adhesive composition for a tire cord, the tire cord and the tire according to specific embodiments of the present invention will be described in detail.
As used herein, the weight average molecular weight refers to a weight average molecular weight in terms of polystyrene measured by a GPC method. In measuring the polystyrene-reduced weight average molecular weight measured by GPC, a known analytical device, a detector (such as a refractive index detector) and an analytical column can be used, and the temperature conditions, solvents and flow rates that are generally applied can be applied.
As a specific example of the measurement conditions, a 0.05% -LiCl/DMF solution for analysis was prepared by weighing 2.12g of anhydrous lithium chloride (LiCl), placing in a 1l volumetric flask and dissolving in N, N-Dimethylformamide (DMF). 0.0250g (25mg) of a sample of a polymer such as a polyurethane resin was added to the vial, and 10ml of 0.05% -LiCl/DMF was added and dissolved. Then, the solution was filtered using a syringe filter having a pore size of 0.45 μm, and 100 μ l of the solution was introduced into GPC as a mobile phase of GPC using LiCl/DMF and introduced at a flow rate of 1.0 mL/min; as a column, 1 Agilent PLgel5 μm Guard (7.5X 50mm) and 2 Agilent PLgel5 μm Mixed D (7.5X 300mm) were connected in series; as detector, an Agilent 1260Infinity II system, RI detector was used; the measurement temperature was 40 ℃.
For the standard substance, 0.0050g (5mg) of polystyrene was added to a vial, 5ml of 0.05% -LiCl/DMF was added and dissolved, and measurement was performed by the above-described method. Calibration curves were plotted by PS 842000, 193000, 65000, 16200 and 4000.
According to one embodiment of the present invention, there is provided an adhesive composition for a tire cord comprising: an epoxy compound; a latex; an alicyclic polyurethane resin having a weight average molecular weight (Mw) of 250,000 to 350,000; an amine compound; and water.
The present inventors confirmed through experiments that an adhesive composition applied to a tire cord cannot sufficiently secure adhesive strength even if it contains a common polyurethane resin, and in the case of using an alicyclic polyurethane resin having a predetermined weight average molecular weight, adhesive strength and heat resistant adhesive strength can be significantly improved, and in particular, high adhesive strength and heat resistant adhesion to a tire rubber can be exhibited, and thus, durability of a tire can be improved, thereby completing the present invention.
More specifically, since the alicyclic polyurethane resin contained in the adhesive composition for a tire cord has a weight average molecular weight (Mw) of 250,000 to 350,000, the adhesive composition for a tire cord may have a viscosity similar to that of latex at room temperature, hydrolysis does not occur even at high temperature, and the composition has high adhesiveness and is stable during stirring.
Specifically, the lower limit of the weight average molecular weight (Mw) of the polyurethane may be, for example, 255,000 or more, 260,000 or more, 265,000 or more, 270,000 or more, 275,000 or more, 280,000 or more, 285,000 or more, 290,000 or more, 295,000 or more, 300,000 or more, or 305,000 or more. The upper limit of the weight average molecular weight (Mw) of the polyurethane may be, for example, 345,000 or less, 340,000 or less, 335,000 or less, 330,000 or less, 325,000 or less, 320,000 or less, 315,000 or less, 310,000 or less, 305,000 or less, or 300,000 or less.
If the weight average molecular weight (Mw) of the alicyclic polyurethane resin is low, the viscosity of the adhesive composition for a tire cord may be relatively low, and thus, sufficient adhesive performance may not be exhibited, and high adhesive strength and heat-resistant adhesion to a tire rubber may not be ensured.
If the weight average molecular weight (Mw) of the alicyclic polyurethane resin is high, the viscosity of the adhesive composition for a tire cord may be significantly increased, and thus, other components may be unevenly mixed, and thus, it may be difficult to ensure uniform adhesive strength. Also, if the weight average molecular weight (Mw) of the alicyclic polyurethane resin is high, the alicyclic polyurethane resin itself may be reacted in advance or with other components to form a gel, and thus, the preparation of a uniform adhesive solution may be disturbed, and appearance defects of the product may be generated.
Meanwhile, the alicyclic polyurethane resin having a weight average molecular weight (Mw) of 250,000 to 350,000 protects or traps an amine compound described below, thus enabling stable curing of an adhesive layer (or coating layer) formed of the adhesive composition. Also, since polyurethane has excellent affinity with rubber or latex components, it contributes to stable adhesion of the adhesive composition to an adherend including rubber, thus ensuring excellent adhesive strength (in particular, heat-resistant adhesive strength) with the adherend. In addition, in the case of using a water-dispersed polyurethane, the abrasion resistance and elasticity of the polyurethane can also be ensured.
The alicyclic polyurethane resin having a weight average molecular weight (Mw) of 250,000 to 350,000 contains an alicyclic structure, and thus, not only mechanical strength and dimensional stability of the adhesive composition for a tire cord and the tire cord prepared therefrom can be improved, but also heat resistance and fatigue properties can be improved.
In contrast, in the case where the adhesive composition for a tire cord includes an aromatic polyurethane resin containing an aromatic group in the molecule, the tensile strength or fatigue resistance of the tire cord produced using the same may be deteriorated, or the uniformity or homogeneity of the adhesive composition for a tire cord may be deteriorated, and thus, the adhesive strength may be deteriorated.
The alicyclic polyurethane resin having a weight average molecular weight (Mw) of 250,000 to 350,000 may include a reaction product between a polyisocyanate including one or more alicyclic groups having a carbon number of 4 to 30 and a polyol, and more specifically, may include a reaction product between a diisocyanate including one or more alicyclic groups having a carbon number of 4 to 30 and including a central group having a total carbon number of 4 to 40 and a polyol.
The cycloaliphatic diisocyanate may be 4, 4' -dicyclohexylmethane diisocyanate (H12MDI), isophorone diisocyanate (IPDI), 1, 4-cyclohexylene diisocyanate or mixtures thereof.
As examples of the polyol, polyester polyol, polyether polyol, polycarbonate polyol and the like can be mentioned.
The alicyclic polyurethane resin having a weight average molecular weight (Mw) of 250,000 to 350,000 may further include: alcohols such as Ethylene Glycol (EG), 1, 4-Butanediol (BD), 1, 6-Hexanediol (HD), Trimethylolpropane (TMP), and the like; and chain extenders such as Ethylenediamine (EDA) and diethanolamine and the like.
Meanwhile, the alicyclic polyurethane resin may be dispersed in water (H)2O) of the polyurethane. The content of water contained in the water-dispersed polyurethane is not particularly limited. For example, the water content in the water-dispersed polyurethane may be 40 wt% to 80 wt%, and other contents may be occupied by the polyurethane. Depending on the circumstances, small amounts of known additives may be included in the water-dispersed polyurethane at a level of about 10 wt% or less, about 5 wt% or less, or about 1 wt% or less.
More specifically, the cycloaliphatic polyurethane resin may be a water-dispersed cycloaliphatic polyurethane resin formed from a cycloaliphatic polyurethane ionomer.
The water-dispersed cycloaliphatic polyurethane resin formed from the cycloaliphatic polyurethane ionomer may be prepared as follows: polyester Polyurethane (PU) is prepared from alicyclic polyisocyanate such as 4, 4' -dicyclohexylmethane diisocyanate (H12MDI), 1, 6-Hexanediol (HD), dimethylolbutyric acid (DMBA), and the like, and neutralized with Triethylamine (TEA), and then dispersed in water and subjected to chain extension with Ethylenediamine (EDA) in water.
More specifically, the alicyclic polyurethane resin may include 1 to 20 mol% of a moiety derived from one or more compounds selected from dimethylolbutyric acid and dimethylolpropionic acid.
In the alicyclic polyurethane resin, a portion derived from one or more compounds selected from dimethylol butyric acid and dimethylol propionic acid links ionic functional groups on the surface of the alicyclic polyurethane resin, thereby improving the degree of stability of the whole molecule during dispersion in water, so that the adhesive composition for a tire cord may have adhesive strength and flexibility at high temperature.
If the content of the moiety derived from one or more compounds selected from dimethylolbutyric acid and dimethylolpropionic acid in the alicyclic polyurethane resin is too small, the polymerization degree of the alicyclic polyurethane resin may decrease or the molecular weight may not be sufficiently ensured.
If the content of the moiety derived from one or more compounds selected from dimethylolbutyric acid and dimethylolpropionic acid in the alicyclic polyurethane resin is too large, the viscosity of the adhesive composition for a tire cord may increase, or sludge (sludge) may be formed in the composition.
Meanwhile, the adhesive composition for a tire cord may include 0.5 to 10 wt% of an alicyclic polyurethane resin having a weight average molecular weight (Mw) of 250,000 to 350,000.
If the adhesive composition for a tire cord includes a low content of the alicyclic polyurethane resin as compared with the epoxy compound, the adhesive property and fatigue property may be deteriorated, and the adhesive property may be significantly deteriorated. If the adhesive composition for a tire cord includes an excessive amount of the alicyclic polyurethane resin compared to the epoxy compound, the concentration of the adhesive composition for a tire cord may be significantly increased, and thus, sludge may be generated or gel may be generated during the application of the adhesive composition, and appearance defects of a product may be generated.
Meanwhile, the adhesive composition for a tire-cord may satisfy a viscosity in a range of 2.50 to 2.85 measured at room temperature using an Ubbelohde viscometer.
"room temperature" is a state in which the temperature is not particularly increased or decreased, and for example, it may mean a temperature in the range of 15 ℃ to 30 ℃. Specifically, within the above temperature range, the room temperature may be a temperature of 17 ℃ or higher, 19 ℃ or higher, 21 ℃ or higher, or 23 ℃ or higher and 29 ℃ or lower, or 27 ℃ or lower.
Also, throughout the specification, unless specifically defined, the temperature at which the evaluation of the numerical properties is performed may be room temperature.
Specifically, the lower limit of the viscosity of the pressure-sensitive adhesive composition may be, for example, 2.51 or more, 2.52 or more, 2.53 or more, 2.54 or more, 2.55 or more, 2.56 or more, 2.57 or more, 2.58 or more, 2.59 or more, 2.60 or more, 2.61 or more, 2.62 or more, 2.63 or more, 2.64 or more, 2.65 or more, 2.66 or more, 2.67 or more, 2.68 or more, 2.69 or more, or 2.70 or more.
The upper limit of the viscosity of the pressure-sensitive adhesive composition may be, for example, 2.84 or less, 2.83 or less, 2.82 or less, 2.81 or less, 2.80 or less, 2.79 or less, 2.78 or less, 2.77 or less, 2.76 or less, 2.75 or less, 2.74 or less, 2.73 or less, 2.72 or less, or 2.71 or less.
In the case where the adhesive composition for a tire cord satisfies the above viscosity range, as shown in the following test, an optimum adsorption rate (pick up rate) can be secured, processability and productivity can be improved, and excellent adhesive strength can be provided.
In particular, it has been confirmed that water (H) is used in consideration of the risk of fire, the harm to the human body, the dispersibility of other components of the composition, and the like2O) instead of organic solventsAs the adhesive composition or the dispersion medium of each component contained in the composition, the viscosity of the adhesive composition may be reduced, and sufficient adhesive strength may not be ensured.
The epoxy compound functions as a curing agent, thus forming a three-dimensional network structure when the adhesive is heat-treated, and imparting adhesive strength and layer stability to a coating layer formed from the adhesive composition.
The kind of the epoxy compound included in the adhesive composition is not particularly limited, provided that the viscosity range of the total composition explained above is satisfied. For example, glycidyl ether compounds such as diethylene glycol-diglycidyl ether, polyethylene glycol-diglycidyl ether, polypropylene glycol-diglycidyl ether, neopentyl glycol-diglycidyl ether, 1, 6-hexanediol-diglycidyl ether, glycerol-polyglycidyl ether, trimethylolpropane-polyglycidyl ether, polyglycerol-polyglycidyl ether, pentaerythritol-polyglycidyl ether, diglycerol-polyglycidyl ether, sorbitol-polyglycidyl ether, and the like; novolac type epoxy resins such as phenol novolac type epoxy resin or cresol novolac type epoxy resin, and the like; and bisphenol type epoxy resins such as bisphenol a type epoxy resin or bisphenol F type epoxy resin, and the like.
Also, known or commercially available epoxy compounds may be used provided that the viscosity range of the total composition described above is satisfied. For example, as the epoxy compound, EX614B from Nagase, KETL6000 from Kolon, CL16 from Ibox Chemicals, GE500 from Raschig, or the like can be used.
The above proposed commercially available sorbitol polyglycidyl ether may have an epoxy equivalent weight (g/EQ) of 120 to 300g/EQ, and if the equivalent weight of sorbitol polyglycidyl ether is less than 120, the polymerized units of the epoxy resin may be small, and thus it may be difficult to form a network structure between isocyanates. Also, if the sorbitol polyglycidyl ether has an equivalent weight of more than 300, the epoxy amount per unit molecule may be relatively insufficient, and thus, the adhesive strength may be deteriorated.
The adhesive composition for a tire cord may include 0.1 wt% to 10 wt% of the epoxy compound.
The latex contained in the adhesive composition for tire cord is a component used in consideration of the use of the composition.
Specifically, the adhesive composition can be used for an adherend component such as a rubber compound, a rubber structure, or a rubber reinforcing material, and in the case of using a latex, it can be advantageous to ensure affinity, compatibility, or adhesive strength with an adherend. According to circumstances, the latex component contained in the adhesive composition may be the same as the rubber component of the adherend.
According to one example, the latex may not comprise resorcinol-formaldehyde or components derived therefrom. That is, the adhesive composition may be an RF-free composition. Therefore, compared to the prior art using RF latex, it is possible to provide an environmentally friendly adhesive composition that is not harmful to the human body. Also, the use of such an adhesive composition has the advantage of reducing the cost of subsequent management and subsequent handling.
The kind of latex that can be used in the adhesive composition is not particularly limited as long as it does not contain resorcinol-formaldehyde or components derived therefrom and satisfies the viscosity of the total composition as explained above.
According to one example, as the latex, natural rubber latex, vinyl-pyridine-styrene-butadiene copolymer latex (VP latex), styrene-butadiene copolymer latex, acrylate copolymer latex, butyl rubber latex, chloroprene rubber latex, or modified latex thereof may be used. With respect to the modified latex, there is no limitation on the method of modifying the latex or the specific kind of the latex. For example, a modified latex obtained by modifying a vinyl-pyridine-styrene-butadiene copolymer with a carboxylic acid or the like can be used.
Commercially available latex may also be used as long as the viscosity of the total composition described below can be satisfied. For example, as the VP latex, commercial products such as LM-60 from Denaka, VP-150 from APCOTEX, VB-1099 from Nippon A & L, or 5218 or 0653 from Closlen, etc. can be used.
According to one example, a latex component comprising one or more of the above latexes may be used in the adhesive composition.
According to one example, the adhesive composition for a tire cord may include 1.0 wt% to 30 wt% of a latex. In the case where the above range is satisfied, it may be advantageous to ensure affinity, compatibility, or adhesive strength with the rubber-containing adherend to which the adhesive composition is applied.
According to one example, the latex may be mixed with the other components of the composition when dissolved in a solvent (water or organic solvent).
The amine compound contained in the adhesive composition for a tire cord functions as a curing agent. A stable coating layer can be formed due to curing or accelerated curing caused by the amine compound.
In the adhesive composition for a tire cord, one or more amine compounds may be used in consideration of a viscosity decrease depending on the use of an alicyclic polyurethane resin having a weight average molecular weight (Mw) of 250,000 to 350,000 and a solvent (water). Specifically, the adhesive composition may include an amine compound having at least a chain structure.
According to an example, the amine compound having a chain structure may be a compound derived from the reaction of ethylenediamine and stearic acid. Here, the carbon number of the amine compound may be 8 to 20 (product name: Acrawax from Lonza)TMC dispersion liquid). The amine compound may be present in a solid state or a liquid state, and in the case where it is present in a solid state, a solvent for dispersing it into a liquid may be used.
Further, the kind of the amine compound is not particularly limited, and according to one example of the present invention, an amine compound that can be used as a curing agent may be used as the amine compound without limitation. As the amine compound, for example, at least one of alicyclic amine, aliphatic amine, and aromatic amine may be used.
More specifically, piperazine from DAEJUNG, G640 from Kukdo Chemical, HK511 from Huntsman Corporation, and the like may be used as the amine compound according to one example of the present invention.
The weight ratio of the amine compound having a chain structure to the alicyclic amine compound may be 1:1 to 3:1 or 7:1 in consideration of the curing acceleration effect of the adhesive composition for a tire cord.
The adhesive composition for a tire cord may include 0.1 wt% to 10 wt% of the amine compound.
The adhesive composition for tire cord may contain water (H)2O)。
Specifically, the adhesive composition for a tire cord uses water as a solvent, not an organic solvent (such as toluene or ethanol), in consideration of the danger to human bodies and the risk of fire. That is, the adhesive composition for a tire cord may be a water-based composition or an aqueous composition.
According to one example, the water used as a solvent in the adhesive composition may be demineralized water.
According to an example, the water content may be 50 wt% or more, or 65 wt% or more, based on the total weight of the composition for which the viscosity is measured. Specifically, the lower limit of the content of water may be, for example, 70 wt% or more, 75 wt% or more, or 80 wt% or more. Also, the upper limit of the content of water may be, for example, 95 wt% or less, 85 wt% or less, or 75 wt% or less. In the case of satisfying the above range, each component constituting the composition may be sufficiently dispersed in the solvent.
According to an example, the amount of water in the total composition may refer to the amount of water mixed as a solvent.
According to one example, the content of water in the total composition may include not only the content of water mixed as a solvent but also the content of water mixed in other components, such as water for dispersing an alicyclic polyurethane resin having a weight average molecular weight (Mw) of 250,000 to 350,000.
Meanwhile, the adhesive composition for a tire cord may further include one or more crosslinking agents selected from the group consisting of isocyanate-based compounds, aziridine-based compounds, and metal chelate compounds.
The kind of the crosslinking agent for imparting adhesive strength and cohesive strength is not particularly limited, and common compounds such as isocyanate-based compounds, aziridine-based compounds, epoxy-based compounds, metal chelate compounds, and the like may be used.
The adhesive composition for a tire cord may contain a crosslinking agent in an amount of 1 wt% to 20 wt%.
When the adhesive is heat treated, the crosslinking agent forms a three-dimensional network structure, thereby imparting adhesive strength and layer stability to a coating layer formed from the adhesive composition.
The kind of the isocyanate is not particularly limited, but may be selected in consideration of the viscosity range of the total composition as described above. For example, as the isocyanate, a compound containing an alicyclic group, i.e., an alicyclic isocyanate can be used. The aromatic polyisocyanate can ensure a high reaction rate compared to the non-aromatic polyisocyanate, and thus, it can be advantageous to increase the low viscosity of the aqueous composition.
According to an example, the aryl group contained in the isocyanate compound may be a phenyl group, and as the isocyanate containing such an aryl group, for example, methylene diphenyl polyisocyanate or polymethylene polyphenyl polyisocyanate (polymethylene polyphenyl polyisocyanate) or the like may be used.
According to one example, the isocyanate compound may be a blocked isocyanate. The blocked isocyanate compound can be prepared by a reaction of adding a known blocking agent to a polyisocyanate compound. As such a capping agent, the following compounds can be used: for example, phenols such as phenol, thiophenol, chlorophenol, cresol, resorcinol, p-sec-butylphenol, p-tert-butylphenol, p-sec-amylphenol, p-octylphenol, p-nonylphenol; secondary or tertiary alcohols such as isopropanol, tert-butanol, and the like; secondary aromatic amines such as diphenylamine and dimethylaniline, etc.; phthalimide; lactams such as delta-valerolactam, and the like; caprolactam, such as epsilon-caprolactam; active methylene compounds such as dialkyl malonates, acetylacetone, and alkyl acetoacetates; oximes such as acetoxime, methylethylketoxime, cyclohexanone oxime, and the like; basic nitrogen compounds such as 3-hydroxypyridine, and acidic sodium sulfite, and the like.
More specifically, commercially available water-dispersed blocked isocyanate products such as IL-6 from EMS, DM-6500 from MEISEI Chemical, and the like can be used as the isocyanate.
Also, a known or commercially available isocyanate compound may be used provided that the above viscosity range of the total composition is satisfied. For example, commercially available water-dispersible blocked isocyanate products such as IL-6 from EMS or DM-6500 from MEISEI Chemical may be used.
Meanwhile, according to another embodiment of the present invention, there is provided a tire cord, including: a fibrous substrate; and an adhesive layer formed on the fibrous substrate, and the adhesive layer is formed of an adhesive composition according to an embodiment.
For the detailed description of the adhesive composition for tire cord according to the above embodiment, the above description is applied.
The adhesive composition for a tire-cord does not contain resorcinol-formaldehyde or a component derived therefrom, and thus is environmentally friendly, and it can significantly improve the adhesive strength or heat-resistant adhesive strength between a tire rubber and a tire-cord, and thus it has high adhesive strength or heat-resistant adhesive strength to the tire rubber, and can improve the durability of the tire. Also, according to the present disclosure, there is provided a tire including the above tire-cord.
Although the specific use of the tire cord is not limited, since the adhesive layer is included, higher adhesion to the hybrid cord can be achieved, and it can be suitably used for large tires requiring higher heat-resistant adhesion.
According to still another embodiment of the present invention, there is provided a tire-cord including: a fibrous substrate; and an adhesive layer formed on the fiber substrate, and including an epoxy compound, a latex, an alicyclic polyurethane resin having a weight average molecular weight (Mw) of 250,000 to 350,000, and an amine compound.
The adhesive composition for a tire-cord does not contain resorcinol-formaldehyde or a component derived therefrom, and thus is environmentally friendly, and it can significantly improve the adhesive strength or heat-resistant adhesive strength between a tire rubber and a tire-cord, and thus it has high adhesive strength or heat-resistant adhesive strength to the tire rubber, and can improve the durability of the tire. Also, according to the present disclosure, there is provided a tire including the above tire-cord.
The alicyclic polyurethane resin having a weight average molecular weight (Mw) of 250,000 to 350,000 may include a reaction product between a polyisocyanate including one or more alicyclic groups having a carbon number of 4 to 30 and a polyol.
The alicyclic polyurethane resin may include 1 to 20 mol% of a moiety derived from one or more compounds selected from dimethylol butyric acid and dimethylol propionic acid.
The fibrous substrate may be a raw cord comprising polyester fibers.
Although the specific use of the tire cord is not limited, since the adhesive layer is included, higher adhesion to the hybrid cord can be achieved, and it can be suitably used for large tires requiring higher heat-resistant adhesion.
Meanwhile, according to still another embodiment of the present invention, there is provided a tire comprising the above tire-cord.
The pneumatic tire may include: a tread portion; a pair of shoulder portions extending to both sides around the tread portion, respectively; a pair of sidewall portions extending to respective shoulder portions; a pair of bead portions extending to respective sidewall portions; a carcass layer formed inside the tread portion, the shoulder portion, the sidewall portion, and the bead portion; a cord located inside the carcass layer; a belt portion located between an inner surface of the tread portion and the carcass layer; and an inner liner bonded to the inside of the carcass layer.
Advantageous effects
According to the present disclosure, it is possible to provide an environmentally friendly adhesive composition for a tire-cord, which can significantly improve the adhesive strength and heat-resistant adhesive strength between a tire rubber and a tire-cord; it is possible to provide a tire cord having high adhesive strength and heat-resistant adhesive strength with a tire rubber, and therefore, capable of improving the durability of a tire; and a tire comprising the above tire cord can be provided.
Drawings
Fig. 1 is a schematic diagram showing the ubbelohde viscometer used in test example 1.
Detailed Description
The present invention will be explained in more detail in the following examples. However, these examples are provided only for illustrating the present invention, and the scope of the present invention is not limited thereto.
Examples and comparative examples: adhesive composition for tire cord and production of tire cord
Example 1
(1) Synthesis of Water-dispersed polyurethane resin
Polyester polyol (weight average molecular weight: 2000), diol (1, 6-hexanediol) and dimethylolbutanoic acid (DMBA) were introduced at the molar ratios shown in Table 1 below and mixed at 75. + -. 5 ℃ under atmospheric pressure for 4 hours.
Then, 4' -dicyclohexylmethane diisocyanate (H) was added in the molar ratio shown in table 1 below12MDI) was added to the mixture and reacted for 2 hours to prepare an alicyclic polyurethane prepolymer.
The reaction temperature of the prepolymer prepared above was lowered to 60 ℃, and a neutralizer (triethanolamine, TEA) was introduced into the solvent (acetone) to disperse. Here, a stirrer is used for dispersion, and the RPM of the stirrer is maintained at 1000 to 1500. After completion of the dispersion, the prepolymer was decompressed to remove acetone.
Distilled water was introduced into the neutralized prepolymer so that the solid content became 60%. Then, a chain extender (ethylenediamine, EDA) was added to prepare a water-dispersed alicyclic polyurethane (weight average molecular weight: 308,000 g/mol).
(2) Preparation of adhesive composition for tire cord
The components were mixed in the content ratios (wt%) as shown in the following table 4, and stirred at a temperature of about 20 ℃ for 24 hours to prepare compositions of each example and comparative example.
(3) Preparation of tire cords
2-ply primary twisted yarns 111 and 112(Z direction) having a twist count of 360TPM were prepared by using polyester yarns, and then the 2-ply primary twisted yarns 111 and 112 were subjected to secondary twisting at a twist count of 360TPM to prepare a plied yarn (1650dtex/2 ply). The thus prepared plied yarn is used as a raw cord 110.
The raw cord 110 composed of polyester is dipped in the first coating solution and then treated at a drying temperature of 150 c and a curing temperature of 240 c for 1 minute to form the first coating layer 211, respectively, thereby providing the reactive groups to the raw cord 110.
Then, in order to provide the adhesive composition to the raw-cord 110 on which the first coating layer 211 is formed, the raw-cord 110 on which the first coating layer 211 is formed is immersed in the second coating solution, and then dried and cured. Herein, drying and curing were performed by treating at a drying temperature of 150 ℃ and a curing temperature of 235 ℃ for 1 minute, respectively. The first coating solution dipping process and the second coating solution dipping process were continuously performed with a tension of 0.5 g/d. Thus, the tire-cord 201 is produced in the form of a dipped cord.
Examples 2 to 10
(1) Synthesis of Water-dispersed polyurethane resin
Water-dispersed alicyclic polyurethane was prepared by the same method as example 1, except that the molar ratio of the components used was changed as shown in the following Table 1 or Table 2.
(2) Preparation of adhesive composition for tire cord
The components were mixed in the content ratios (wt%) shown in the following table 4 or table 5, and stirred at a temperature of about 20 ℃ for 24 hours to prepare respective compositions.
(3) Preparation of tire cords
A tire cord was produced by the same method as example 1, except that the adhesive composition for a tire cord was changed.
Comparative examples 1 to 5
(1) Synthesis of Water-dispersed polyurethane resin
Water-dispersed alicyclic polyurethane was prepared by the same method as example 1, except that the molar ratio of the components used was changed as shown in the following Table 3.
Here, the weight average molecular weights of the water-dispersed alicyclic polyurethane resins used in comparative examples 1 to 4, respectively, are shown in table 3, and methylene diphenyl diisocyanate (MDI) aromatic diisocyanate was used instead of 4, 4' -dicyclohexylmethane diisocyanate in comparative example 5.
(2) Preparation of adhesive composition for tire cord
The components were mixed in the content ratios (wt%) as shown in the following table 6, and stirred at a temperature of about 20 ℃ for 24 hours to prepare respective compositions.
(3) Preparation of tire cords
A tire cord was produced by the same method as example 1, except that the adhesive composition for a tire cord was changed.
[ Table 1]
(unit: molar ratio) Example 1 Example 2 Example 3 Example 4 Example 5
(A) Polyester polyols 1 0.5 2 1 1
(B) Dihydric alcohol 0.2 0.2 0.2 1 2
(C)DMBA 0.8 0.8 0.8 0.8 0.8
(D)H12MDI 2 2 2 2 2
(E)EDA 1 1 1 1 1
(F)TEA 7 7 7 7 7
Mw(g/mol) 308,000 286,000 346,000 316,000 322,000
[ Table 2]
(unit: molar ratio) Example 6 Example 7 Example 8 Example 9 Example 10
(A) Polyester polyols 1 1 1 1 1
(B) Dihydric alcohol 6 8 0.2 0.2 0.2
(C)DMBA 0.8 0.8 3 0.8 0.8
(D)H12MDI 2 2 2 2 2
(E)EDA 1 1 1 4 1
(F)TEA 7 7 7 7 5
Mw(g/mol) 337000 342000 299000 319000 299000
[ Table 3]
(unit: molar ratio) Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5
(A) Polyester polyols 0.1 2.5 1 1 1
(B) Dihydric alcohol 0.2 0.2 0 12 0.2
(C)DMBA 0.8 0.8 0.8 0.8 0.8
(D)H12MDI 2 2 2 2 -
(D)MDI - - - - 2
(E)EDA 1 1 1 1 1
(F)TEA 7 7 7 7 7
Mw(g/mol) 231000 364000 217000 379000 315000
[ Table 4]
(unit: wt%) Example 1 Example 2 Example 3 Example 4 Example 5
(A) Latex 14.7 14.7 14.7 14.7 14.7
(B) Water-dispersible polyurethanes 1.5 1.5 1.5 1.5 1.5
(C) Amine compound 1.8 1.8 1.8 1.8 1.8
(D) Chain extender 0.4 0.4 0.4 0.4 0.4
(E) Epoxy compound 1.7 1.7 1.7 1.7 1.7
(F) Isocyanates 3.4 3.4 3.4 3.4 3.4
(G) Solvent(s) 76.5 76.5 76.5 76.5 76.5
TSC 23.5 23.5 23.5 23.5 23.5
[ Table 5]
(unit: wt%) Example 6 Example 7 Example 8 Example 9 Example 10
(A) Latex 14.7 14.7 14.7 14.7 14.7
(B) Water-dispersible polyurethanes 1.5 1.5 1.5 1.5 1.5
(C) Amine compound 1.8 1.8 1.8 1.8 1.8
(D) Chain extender 0.4 0.4 0.4 0.4 0.4
(E) Epoxy compound 1.7 1.7 1.7 1.7 1.7
(F) Isocyanates 3.4 3.4 3.4 3.4 3.4
(G) Solvent(s) 76.5 76.5 76.5 76.5 76.5
TSC 23.5 23.5 23.5 23.5 23.5
[ Table 6]
Figure BDA0003643543130000151
< descriptions of tables 4 to 6 >
(A) Latex: VP latex 0653 from Closlen
(C) Amine compound: acrawax from LonzaTMC dispersion (D) chain extender: piperazine derivatives
(E) Epoxy compound (c): EX614B from NAGASE (sorbitol polyglycidyl ether, epoxy content: 167g/eq, viscosity (mPas): 21,200)
(F) Isocyanate: IL-6 from EMS
(G) Solvent: softened water
TSC: total solid content
[ test examples ]
Test example 1: measurement of viscosity of compositions of examples and comparative examples
The viscosity of each composition of the examples and comparative examples prepared above was measured at room temperature (about 25 ℃) using an Ubbelohde viscometer.
The composition was placed in a constant temperature water bath (about 25 ℃) for 30 minutes, and then measured using an Ubbelohde viscometer. Specifically, by the following procedure, a certain amount of demineralized water was added to an Ubbelohde viscometer and the viscosity property of the demineralized water was measured, and the viscosity property of the composition was measured by the same method, and then the relative viscosity was calculated based on the viscosity property of the demineralized water which had been measured.
The specific measurement method of the viscosity is as follows, and the measurement results are shown in table 7.
(1) The sample (composition or demineralized water) was introduced into the a-tube of the ubbelohde viscometer.
(2) After setting the constant temperature water bath at 25 ℃, it was fixed, part C was immersed in the water bath, and left to stand for 30 minutes.
(3) The sample was positioned to the middle of section C using a pipette.
(4) The sample flowed down and the time from when the sample level passed the upper tick mark of B until the sample level passed the lower tick mark of B was measured.
(5) The measured time is applied to a relative viscosity calculation formula to calculate the relative viscosity.
< formula for calculating relative viscosity >:
T1/T0
t1: time T0 from when composition passed the upper tick mark of B until composition passed the lower tick mark of B: from when the softened water passes the upper scale line of B until the softened water passes the lower scale line of BTest example 2: evaluation of adhesive Strength
For each of the tire cords prepared in examples and comparative examples, in order to evaluate the adhesive strength per unit area, the adhesive peel strength of the tire cord was measured according to ASTM D4393. Specifically, a rubber sheet having a thickness of 0.6mm, a cord layer and a rubber sheet having a thickness of 0.6mm were sequentially laminated to prepare a sample, which was then subjected to 60kg/cm at 170 ℃2Was vulcanized for 15 minutes under pressure to prepare a sample.
Then, the vulcanized sample was cut to prepare a sample having a width of 1 inch. For the prepared test pieces, the adhesive strength of the tire cord was measured by testing the peel strength at a speed of 125mm/min at 25 ℃ using an universal tester (Instron). Here, the average value of the load generated during peeling was evaluated as the adhesive strength. The adhesive strength was evaluated and summarized in table 7 below.
Test example 3: evaluation of thermal fatigue resistance
For each of the tire cords prepared in examples and comparative examples, fatigue resistance of each of the compositions of examples and comparative examples was measured.
Specifically, a rubber sheet having a thickness of 0.6mm, a cord layerAnd a rubber sheet having a thickness of 0.6mm were sequentially laminated to prepare a test specimen, which was then subjected to 60kg/cm at 170 deg.C2Was vulcanized for 15 minutes under pressure to prepare a sample. Then, the vulcanized sample was cut to prepare a sample having a width of 1 inch. The fatigue properties of the prepared specimens can be evaluated by observing the unflexed portions and the flexed portions of the tire cord mat specimens, the adhesive strength of the rubber compound to the tire cord, and the interface.
In a fatigue tester, a specimen having a width of 1 inch was attached, and then preheated at 100 ℃ for 30 minutes. Then, the tester conditions of 100,000 cycles at 180rpm and 60kg load were established, and a 1-inch Flexing Roller (Flexing Roller) was used. After the fatigue evaluation was completed, the test specimen was taken out of the testing machine and left at room temperature for 12 hours, and then peel strength test was performed at 25 ℃ and 125mm/min using a universal testing machine (Instron).
The thermal fatigue resistance was measured according to the following formula 1, and the results thereof are shown in the following table 7.
[ formula 1]
Fatigue (%) (measurement of adhesive strength for flexed portion) × 100/(measurement of adhesive strength for unflexed portion)
[ Table 7]
Viscosity (RV) Adhesive Strength (%) Thermal fatigue resistance (%)
Example 1 2.71 100 100
Example 2 2.64 97 100
Example 3 2.82 97 98
Example 4 2.73 100 99
Example 5 2.76 100 95
Example 6 2.79 100 95
Example 7 2.81 100 99
Example 8 2.74 100 100
Example 9 2.54 100 97
Example 10 2.60 99 98
Comparative example 1 2.41 75 72
Comparative example 2 2.88 75 79
Comparative example 3 2.44 72 81
Comparative example 4 2.89 76 80
Comparative example 5 2.92 77 79
As shown in table 7, it was confirmed that: the adhesive composition for a tire cord of the example has a viscosity in the range of 2.50 to 2.85, and when applied, can improve the adhesive strength of the tire cord to a carcass layer and ensure excellent heat resistant adhesive strength and thermal fatigue resistance.
On the contrary, it was confirmed that: when the adhesive composition for a tire cord of comparative example was applied, sufficient adhesive strength of the tire cord to the carcass layer could not be secured, and the heat resistant adhesive strength and the thermal fatigue resistance were relatively low.

Claims (16)

1. An adhesive composition for tire cords comprising: an epoxy compound; a latex; an alicyclic polyurethane resin having a weight average molecular weight (Mw) of 250,000 to 350,000; an amine compound; and water.
2. The adhesive composition for a tire cord according to claim 1, wherein the alicyclic polyurethane resin having a weight average molecular weight (Mw) of 250,000 to 350,000 comprises a reaction product between a polyisocyanate containing one or more alicyclic groups having a carbon number of 4 to 30 and a polyol.
3. The adhesive composition for a tire cord according to claim 1, wherein the alicyclic polyurethane resin is a water-dispersed alicyclic polyurethane resin formed of an alicyclic polyurethane ionomer.
4. The adhesive composition for a tire cord according to claim 1, wherein the alicyclic polyurethane resin contains 1 to 20 mol% of a moiety derived from one or more compounds selected from dimethylolbutyric acid and dimethylolpropionic acid.
5. The adhesive composition for tire cord according to claim 1, wherein the viscosity measured at room temperature using an Ubbelohde viscometer is in the range of 2.50 to 2.85.
6. The adhesive composition for a tire cord according to claim 1, wherein the adhesive composition comprises 0.5 to 10 wt% of the alicyclic polyurethane resin having a weight average molecular weight (Mw) of 250,000 to 350,000.
7. The adhesive composition for tire cord according to claim 6, wherein the adhesive composition comprises:
0.1 to 10 wt% of an epoxy compound;
1 to 30 wt% of a latex;
0.5 to 10 wt% of an alicyclic polyurethane resin having a weight average molecular weight (Mw) of 250,000 to 350,000;
0.1 wt% to 10 wt% of an amine compound; and
50 to 95 wt% of water.
8. The adhesive composition for a tire cord according to claim 1, wherein the amine compound comprises an amine compound having a chain structure.
9. The adhesive composition for tire cord according to claim 1, wherein the adhesive composition for tire cord further comprises one or more crosslinking agents selected from the group consisting of isocyanate-based compounds, aziridine-based compounds and metal chelate compounds.
10. The adhesive composition for a tire-cord according to claim 1, wherein the adhesive composition for a tire-cord comprises 50% by weight or more of water.
11. A tire cord comprising:
a fibrous substrate; and
an adhesive layer formed on the fibrous substrate and formed from the adhesive composition of claim 1.
12. A tire cord comprising:
a fibrous substrate; and
an adhesive layer formed on the fibrous substrate, and the adhesive layer includes an epoxy compound, a latex, an alicyclic polyurethane resin having a weight average molecular weight (Mw) of 250,000 to 350,000, and an amine compound.
13. The tire cord of claim 12 wherein the cycloaliphatic polyurethane resin having a weight average molecular weight (Mw) of 250,000 to 350,000 comprises the reaction product between a polyisocyanate comprising one or more cycloaliphatic groups having a carbon number of 4 to 30 and a polyol.
14. The tire cord of claim 12 wherein the cycloaliphatic polyurethane resin contains from 1 to 20 mole% of moieties from one or more compounds selected from dimethylol butanoic acid and dimethylol propanoic acid.
15. The tire cord of claim 12 wherein the fibrous substrate is a raw cord comprising polyester fibers.
16. A tire comprising the tire cord of claim 12.
CN202180006471.1A 2020-04-09 2021-04-07 Adhesive composition for tire cord, tire cord and tire Pending CN114729245A (en)

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